Condensation product



Patented Apr. 18, i944 2,316,928 CONDENSATION PRODUCT Eugene Lieber, Staten Island, N. E, assignor to Standard ration of Delaware No Drawing. Original 1939, Serial il Development Company. a corpoapplication November Iii,

No. 304.781, now Patent No 2,268,410, dated December 30, 1941. Divided and this 400,659

8 Claims.

This invention relates to improved condensation products and more particularly to novel waxmodifying agents especially useful as pour depressors, and to methods of preparing same. I

It is known that certain alkyl aryl ketones which might also be called. fatty acid keto aromatics, such as stearo-phenone, have some pourdepressing properties when added to lubricating oil; i. e'., they have some tendency to reduce the pour point of the lubricating oil as determined by the standard A. S. T. M. method. However,

these materials are relatively weak and ineifec-" tive. It has now been found, and is a primary object of the present invention, that the pour depressant potency of such materials can be very greatly improved by condensation with a low molecular weight acyl halide, such as, acetyl chloride. It has also been found, and is a further object of this invention, that the resultant .di-acylated product can be made directly in one operation by acylating a suitable aromatic compound, such as benzene, naphthalene, etc., with a mixture comprising two different acyl halides, one of which is of high molecular weight, having preferably above 15 carbon atoms, while the other is Y of low molecular, not higher than 10 carbon atoms and preferably not higher than 7 carbon atoms, for example, a mixture of stearyl chloride and acetyl chloride.

One example of a method of carrying out the present invention is to condense 1 mol of steamphenone' (prepared by condensing stearyl chloride with benzene) with 1 mol of acetyl chloride in the presence of aluminum chloride, the resulting acetyl stearo-phenone is isolated and is found to be a potent pour depressor. An alternative method of preparing the acetyl stearophenone is to react 1 mol of benzene with a mixture consisting of 1 mol of stearyl chloride and 1 mol of acetyl chloride, in the presence of aluminum chloride. Although it is not known with certainty, it is believed that the chemical reaction involved in the present invention may be represented by the following chemical equations:

carbon atoms and Ar is an aromatic nucleus, such as benzene, naphthalene, etc.

application July 1, 1941, Serial No.

Equation 2 RCOAr+R'COCl- RCOArCOR' in which R. is an alkyl group having less-than 10 5 carbon atoms.

Anrrnmrrvr MITILIOD B Equation 3 (@8'8854-1: Rcoiuoon' For these reactions R should be an alkyl group having at least 10 carbon atoms, and it is preferred that R. be an alkyl group having at least carbon atoms such as obtainable in the fatty.

l5 acids derived by oxidation of paraflln wax, or in fatty acids such as stearic, palmitic, oleic, cerotic, montanic, behemic, etc. obtainable from animal and vegetable fats; The aromatic group Ar should preferably have not more than 3 nuclei and may comprise benzene, naphthalene, anthracehe, phenanthrene, diphehyl, and the like, or mixtures thereof, although substituted aromatic hydrocarbons having a substituent of such a nature as not to interfere with the Friedel- Crafts catalyst, i. e., remaining inert during the Friedel-Crafts condensation, may be used, e. g., alkyl, aralkyl, isocyclyl (e. g. cyclohexyl) halogen, alkoxy, aroxy groups and perhaps hydroxy--but not carboxyl, carbalkoxy, nitro, cyano,"etc.,'R' is 30 preferably an alkyl group having less than 6 carbon atoms such as in the groups: caproyl, valeryl and butyryl, and still better, less than 3 carbon atoms, such as in the acetyl and propionyl groups.

Equations 1, 2 and 3 involving the condensation of 1 or more acyl halides on an aromatic nucleus are preferably carried out in the presence of a suitable Friedel-Crafts type catalyst, such as aluminum chloride; other catalysts include boron fluoride, zinc chloride, iron chloride, titanium tetrachloride, boron chloride and even anhydrous hydrogen fluoride.

The reaction is also preferably carried out in the presence of a suitable inert solvent or a diluent, such as a kerosene or naphtha which has been highly refined by treating with strong sulfuric acid or aluminum chloride. Other solvents include tetrachlorethane, dichlorbenzene, carbon disulflde, nitrobenzene, and the like, or mixtures of any of these.

Reaction usually takes placeat room temperature and is preferably allowed to proceed at room temperature until the vigor of the reaction begins to subside, at which time the reaction liquid is gradually heated to a suitable temperature such 55 as about 220 F. and kept there for a suitable a mol of low molecular weight acyl groups to 1 mol of each of the other two groups.

assaeeo believed to be essentially an acetylated stearyl benzene.

Other tests were carried out in a similar manner except with variations as to the solvent used, the aromatic nucleus used, and the acyl group used, and the pour depressor potencies of the product were tested by blending in a waxy oil having a pour point of +30 F., the pour point being tested by the standard A. S. T. M. procedure. The results of these various tests are summarized in the following table:

Table Pour depressing properties of compounds hav- The products of the present invention are 5 8 the n al ormula potent pour depressors and are therefore particularly suited for addition in man amounts, CO such as .02% to 10% or preferably 0.1% to about in which 3%, towaxy lubricating oils such as tho de- R represents an allwl group having more than 10 rived from Pennsylvania type crude oils or other ar n a om oils rich in parafllnic-type hydrocarbons. Ar is an aromatic group, and g The product of the present invention is also R is an alkyl group having not more than- 10 useful as a wax-modifying agent for other purcarbon atoms. poses, such as an aid for settling, filtering and Weight (g.) of materials used:

Bscyl chloride 5 mg? Solvent A101: Yield Color Product 531 Type G. 0. Mol

Ar=aig.benune==1mol Grams Grams F. 1 Bteeryl s1 24 1 None..-. so as Green.. on -1o 2. BtearyL.-. 87 34 l Kerosene. 80 98 ...do ..do 0 a. Stearyl 87 24 1 CrHsOh" 8O 38 Brown.- Tacky resin 1s 4. Wax-sold s7 12 x Kerosene.. 40 so do on 15 Ar= 62 g. naphthslene=1 mol s. Btesryl s1 s2 1 O'Hl 12 do In -1e 1 Wax-acid chloride made by trestingwith P01: the fatty acids obtained from oxidation of geraiiin war. l'igures show pour point oiblend oi2%oiproductinwaxy oil havingapcur point of +30 Example Twenty-four grams of acetyl chloride (1 mol) were dissolved in 24 grams of benzene (1-mol) To this was added one molar proportion of stearyl chloride prepared by treating 87 grams of stearic acid with 35 grams of P013. Eighty grams of A161: were slowly added with suitable agitation. After the addition of the AlCla, the reaction mixture was heated to 200' F. and maintained thereat for 3 hours. At the end of this time, the reaction mixture was cooled, diluted with kerosene, and neutralized with a mixture of alcohol and water. After settling, the kerosene extract was distilled with fire and steam to 600 F. in order to remove solvent and low boilins products. A bottoms residue comprising grams of a very viscous green oil was obtained as'products. Although the exact structure of the Product is not.known with certainty.

The results in the above table show that the products of this invention when added in amounts of 2% to a waxy-lubricating oil having a pour point of 30 F. effected a reduction in the pour point ranging from 30 to 45' F.

For the sake of comparison, some additional tests were made in which an aromatic nucleus such as benzene or naphthalene, was condensed with two mols of a high molecular weight acyl halide instead of one high molecular weight one and one low molecular weight one according to the present invention. The results in all cases were definitely inferior to those obtained according to the present invention under com parable conditions. For comparison with Examples 1, 2 and 3, two mols of stearyl chloride were reacted with one mol of benzene, and 2% of the resultant distearyl benzene when blended with the same waxy lubricating oil used in Tests 1 to 5, gave a pour point of +20 F., whereas the product of the present invention in Examples 1, 2 and 3, reduced the pour point to 10, 0 and 15 F. respectively. Similarly, 2% of a diwaxed ketone of benzene (reaction product of-- This application is a division of application it 18 1' Serial Nd. 304,781, filed November 16, 1939.

It is not. intended that this invention be limited to any of the specific examples which have been given for the sake of illustration only, nor

to any theory as to the mechanism of the operation of the invention, but only by the appended claims in which it is intended to claim all novelty inherent in the invention as broadly as th rior art permits.

I claim:

1. The process which comprises reacting about 1 mol of a condensible aromatic compound having 1 to 3 nuclei with a mixture of acyl halides, comprising about 1 mol of an acyl halide having more than 10 carbon atoms and about A; to 1 mol of an acyl halide having not more than 10 carbon atoms, in the presence of a Friedel-Crafts catalyst at a temperature between the approximate limits of room temperature and about 220 F., decomposing and removing the catalyst, and distilling the reaction products with fire and steam distillation up to about 600 F. to obtain the desired distillation residue.

2. The process of preparing di-acylated aromatic compounds having wax-modifying properties, which comprises essentially dissolving about 24 parts by weight of acetyl chloride and about 87 parts by weight of stearyl chloride in about 24 parts by weight of benzene in the presence of ethylene dichloride as solvent, slowly adding about 80 parts by weight of aluminum chloride with agitation, at about room temperature, heating the mixture to about 200 F. and maintaining the reaction mixture at about that temperature /2 to 1 mol of an acyl group having for about three hours, cooling the reaction mixture and diluting the same with a low boiling inert diluent, neutralizing and removing the aluminum chloride and distilling the reaction prodnets with fire and steam to about 600 F. to remove solvent and low boiling products and to obtain the desired condensation products as distillation residue.

3. The process which comprises acylating about 1 mol of a ketone having the general formula R-CO-Ar, in which R is an aliphatic group having at least 10 carbon atoms and Ar is an aromatic hydrocarbon group, with about the general formula RCO, in which R' has less than 10 carbon atoms, in the presence of a Friedel-Crafts catalyst, at a temperature between the approximate limits of room temperature and 220 F., neutralizing and removing the catalyst and distilling the condensation products with fire and steam to about 600 F. to obtain the desired mixed di-acylated aromatic hydrocarbon as distillation residue.

' 4. The process according to claim 1 in which the lower acyl halide contains an alkyl group having less than 6 carbon atoms.

5. The process according to claim 1 in which the" lower acyl halide contains an alkyl group having less than 3 carbon atoms.

6.'- Product of the process defined in claim 1.

' 7. Product of the process defined in claim 2.

8. Product of the process defined in claim 3.

EUGENE LIEBE'R. 

